Photographic elements containing azo dyes and process using them



Patented Sept. 30, 1952 PHGTQGRAPHIC ELEMENTS CONTAINING AzonYEsANnPRocEss USINGJrHEM Bela Gaspar, Beverly Hills, ana raulinenielinreyfusstvan- Nuys' calif assignors; by mesne assignments; to:said;Gaspal-' No Drawing. Application April 2, 1948,

Serial No. 18,714

reclaims; (Cl. 95 6) 1,A This invention relates to color photography, and particularly to azo dyes for incorporation: in photographiezlayersi Processes: of: color: photueraphy depending upon the decolorizatlonsofiidyes 1n the presence of metallic silver areiwell known-.. A process of this type in which azodyes are employed in multi-layer coatings: to: produce. colored images by bleaching; the; dyes; in: the: presence of silver imagesiszdiscl'osedi in.- aznum-- benrof: patents; i; e., U Se Patent 2 020;7515; In this process azor' dyes. are uniformly" distributed in photographic colloids'gpreferab'ly' gelatina-silyer halide emulsions; and these; are coated: on: a transparent or: opaque: support; Their material is exposed. and"v developed; and is: them subjected to the action of a bath which destroys the; dye locally? in: the: presence; of: the" metal? deposit? of the photographic image. This results in the pro'ductioni'offa dyetimage whiclrzis-reversednwitlr respectzto the:metal;image.-l

An azo dye must fulfill a numberi oi: requirements in: order. to: make: it; useful: tor." color: photographic purposes. Some of: these-conditions are: The: dyes: must? be stable to photo graphicmrooessing; baths; and: the spectral qualttiesotrthe: dyes: must." satisfycertain" requirements: Aksurvey of; the: heretofore. known azo dyes; the-..remarl able fact that the: numher of brilliant. azo: dyes which: absorb the? blue or the green light is quite large. but that there are. onlyya very limitednumber: of brilliantwazo' dyes which absorb in the longer wave range of the visible spectrum. Most of'thetdyesiwhich' absorb in the longer wave: range are found in the group of those-azo: dyestwhichcontaina an" accumulation of. several GZOrEIOHPS'. This ac cumulation, in most cases, has the. consequence that. besides a shift of r the: absorptionumaximum to longer wave lengthe the; absorption band-is broader; that: is; thedye. becomes? dull 1 on black- 1th..

lit'i is,', therefore, an object: oil the present. invention to. provide photographic layers. containmagenta. .vl'o1et' andblhetdyeswhicli .are. fast to light. and. have desirable spectralv characteriistiSL. Itc has; been found that the dyes! ofthe' generall formula Af -N -:NB'-- N- N-'-A are 2*: i very valuable for color photographic purposes Inrthis general formulaB- stands for arr-aromatic residue carrying the azo bonds shown: inn 114: position,- and A andAf stand-for 'az' H components having in the 2"- or lT os'tibtl.x

the azo: group i a hydroxy ammormonoalliylatnind or arylamino radicals The residueB iacoordirig to this definition, can loe e. g.,.a .paraepherlylerie or a l'A-naphthylene residue 'wiiiehmay carry such substituents as'halogen, ,alRyLjalk substituted'a'illoxy groups; lar-yloicy groups; or. solubilizing groups such as sul'f'oniclacicl'oi car: b'ox-yl groups, or combinations of theselsfiib;

stituent's; Ithasbeen found thati dyes' iii the. residue has ether. substitue'ritsg" s'ii s alkoxy, substituted. alkoxyi' and"aryloizy. grout; are exceptionallywell suitdfdrtli invention; The residues A- and A representithe resiilhesor benzene, naphthalene, pyrazolorie andtlie. like.. having, 'in' the. 2- or the. 4 po'sitiim' to the group, a hydroxy',, an amino; a" moiioalliylja iriiiio or. an. .aryl'amlno, group, Coupling components AandA" which contain iaJliSftl'ro'iiyv fdlipi;ifim 2'- or. ii-position to the ia'zogro'upj are 'niost'ipie; ferre'dl- These residues" A, ar'idf A" mayeoht further substituents such as halogen, hyTdijoiiyiz alkoxy amino, alkyl'amih'o, ems-min acylaiinirldj sulfonic acid,rand carboxyl grcupglairdtiieymay contain. one or' more" furtl'ie, jazoigro i ps Amihona htholsulfon ic;'acids",;pref amy derivm: t'ives or L81 aminonaphthols, such 'aslid. S-acid; at least one of'wliicli" carriesfa'n N-acyl? group, have been found to "produce exceptional?- I'yjsuita'bl'e' dyes when used as thec'oup'lih f som ponents AaiidfA i I f I,

These dyes; are exceptionally Bright" and r, a great brilllanceo'fh'uej and theabs'orptioir y ofthesedyes have .a' very steep, increment: y dye "gelatin to exceil'entgcyan', hlil e; jvicl magenta colors of great clarity a f {excellent stability. They bleach" with great; ease i'n th presence of" agents which" form; reducing pounds by reaction with the nietallicfs v posit. Suitable" agents ror fliisb'le'aqhine nro c: ess are described" in U; s, Patent zlozdflfifl and subsequent patents su'oh as Rlez'ajw'wand $410,025.. "he ,v i.

It is remarkable that dyes of the indicated structure proved so valuable. It is particularly surprising to find brilliant and stable cyan dyes in this class of comparatively simple compounds. Most of the cyan azo dyes so far known are tris or tetrakis azo dyes. Those known cyan azo dyes which are of a more simple structure, as e. g., the cyan mono-azo dyes, are pH sensitive or they are cyan only if they are dissolved in certain organic solvents. It could not be predicted that the dyes of the present invention, even when they contain only the number of azo groups shown in the above formula, would have all the prgperties required for color photographic application. This unexpected result supposedly is due to'the presence of the resonance system Hutpnng aaaa where a: and represent one of itheintegers 1 or' 2, and where Y and Y represent a hydroxy,

an amino, a monoalkyl amino or arylamino. For

instance, in the dye of Example 2 below, the. resonance system OCH: N o

Ho l=l N=N Melina CHp. l r i fi i i ":so'me dyes or this group do not di-iiuse, which means they 'do not wander through set gelatin. Otherswhich do diffuse can be transformed into insoluble? salts ,1 i. e., by addition to the gelatin ofjo'rganic" bases according to U. S. Patents 2,046,Q67;.2,3 17;184- or 2,368,647.

following four methods may be employed in thep'reparation of the dyes:

1. Onefmolofa para-tetrazo compound is coupled'withItwdmols of an azo coupler. "2 One mol of fa para-amino diazo compound is coupled withone mol of an azo coupler. The resulting amino azo dyeis diazotized'and coupled withjoneiurther mol of an azo coupler. The second azo coupler may be identical with or differ fromth'efirst azo coupler. I

3. Qnemol of atpara-acyl'amino diazo'com-v pound is c'oupledwith one mol 'of anazo coupler. The acylamino azo dye thus formed is hydrolyzed to give anj'amino azodye which is diazotized and coupledwith one further mol of an azo coupler. I14, ,Thei 'amino azo dye used'as intermediate in theni'ethods 2 and 3 can be prepared by coupling onemol of a para-nitro diazo compound with one m'ol' of an azo coupler and then reducing the resuiting nitroazo dye.

The usefor' photographic purposes of azo dyes whichare'prepared by coupling tetrazonium salts with'phenols' orfwith alpha-naphthols is already known. However, thetetrazo compounds heretof0reused are derivedfrombicyclic diamines containing the two amino groups in separate rings. The dyes used according to ourinvention are different from those already used, because they contain the azo groups in the same ring.

There are other disazo dyes known for photo-' graphic purposes which difier from the dyes used according "to our invention by lacking in one of the terminall-components of a free hydroxyl, ai'r'iino, monoalkyl'amino or 'arylamino group, in acre-position to the azo group. 7

, Diazo or tetrazo compounds suitable for use in theffproducti'on of the dyes used in the present inventionlcan be obtainedby diaz otation or tetrazot'atio'n" respectively of" amino compounds, of which the following are some examples:

4 1,4-phenylenediamine 5-nitro-2-amino-p-xylene 2,6-dichloro-4-nitraniline 3-bromo-5-nitro-2-aminotoluene 4-acetylaminoaniline-2-sulfonic acid. 4-nitraniline-2-diethylsulfonamide 5-nitro-2-aminobenzylsulfonic acid 1,4-naphthylenediamine-2-sulfonic acid 4-nitro-l-naphthylamine-G-sulfonic acid 5-nitroanthranilic acid ethyl-(5-nitro-2-aminophenyl) -sulfone 4-acetylamino-5-methoxyaniline-2-sulfonic acid 2-benzyloxy-5-chloro-4-nitraniline 4- nitran'iline-2-oxyacetic acid its esters and amides 1 f I 2,5 dimethoXy-l-nitraniline l oxalylamino-2,5-di-(2-hydroxyethoxy) -ani line, its esters and ethers 1 oxalylamino-Z+ethoxy-4-naphthylamine 7 sulfonic acid 2-amino-5-nitrodiphenyl ether ..'Other examples are readily apparent to one skilled in the art.

The diazonium and tetrazonium salts prepared from these amines are combined with azo couplers. From the many types of suitable azo couplers, we may mention the following:

Acetoacet-o-chloroanilide Phenol 1 D-cresol I l-methyl-ZA-dioxo-1,2,3,4-tetrahydroquinoline H Alpha-naphthol a Beta-naphthol n Methylaniline Z-methylindole 3-benzoylaminopheno1, 5-aminophenol-2-sulfonic acid l-(4-sulfophenyl)-pyrazolone (5) 3 carbonic. acid (tartrazinogenic sulfonic acid) l-naphthol-7-sulfonic acid 2-naphthol-3,6-disulfonic acid (R-acid) 1,8 dihydroxynaphthalene -3,6 disulfonic -aci'd (chromotropic acid) chromotropic acid:mono"-:' ethyl ether v.4 8-ch1oro-l-hydroxynaphthalene 3,6 disulfonic acid H I 1-naphthylamine. 6 sulfonic acid (Cleve acid): 1-anilinonaphthalene-8-sulfonic acid (p'henyl-' 8-amino-1-naphthol-5-sulfonic acid (S-acid) 8-amino-1-naphthol-3,5+disulfonic acid -(K-acid) 8-amino-l-naphthol-3,6 disulfonicacid (H-acid) 5-amino-1-naphthol-3-sulfonic acid (M acid): 8-amino-1 -naphthol 5,7 disulfonic' acid (SS- '7-amino-l-naphthol-3-sulfonic acid calm-a acid) N- (phenyl-J-acid) N-(p-toluenesulfo) -K-acid N-'(2,4 -dich1orobenzoyl) -K-acid- 1 5-(p-'sulfophenylazo-)-6-amino 1 naphthol 3-sulfonic acid N-(p-aminophenylacetyl-) I-I acid N-(Z-aminoethyl) -gamma-acid N-(3-chloro-2-hydroxy-nepropyl)-J acid1 t I The disazo dyes obtained from these compo nents can be further treated, e."'g., those gdyes having free amino groups (besides thosearriirio groups in ortho or para position to the "azo groups), may be acylated'by the actionof mono or polycarbonic acid chlorides; anhydrides, suliochlorides or otheracylating agents, suchas 5. aceticanhydride; phthalyl chloride; naphthalene 1,d vilsuli'oclil'or-i'd'e, ketene; etc; or they-"may be diazoti'sed and coupled with azo coupl'ers on they: maybe treated-with phosgene or withaldehydes. The treatment with phosgene; a1dehydes,:e;-g.,-

formaldehyde and its equivalents onwlth one of a is obtained by diazotizing p-nitraniline-o-sulfonic acid, coupling in acid solution with N- ethyl gamma-acid; reducingr in alkalime: solution with sodium sulfide, diazotizing, and coupling; again with-N-ethyl-gamma-acid. The dye, after suitable purification to: remove; products lisg ready forg-usein color photography. ThB-SdilllIt= salt of. the dyeistvery water;soluhle ,,,-.which-meme? ":tates; incorporation in photographic emulsion layers, and also; causeslittleor. no. desensitiza tion-of the. emulsion. In addition, thedye; is;

' quite stable to light and has excellent color'cha'r groups have low molecular weights. The-essen. I tial advantage of this building principle is that the dyes do not diifuse, and that they break down in the dyebleach into compounds which are easily washed out from the photographic colloid.

It is obvious that any two nuclei of two dye; molecules can be linked in the. same: way as: is;

done with the nuclei A and A in the formula.

above. Suitable reactive groups in a monomeric acteristics. It, i'sjai'vivid blue-green, absorbing" nearly no light. ata wavelength. of 5.00..mu, and; the, density even at 570 mu beinglesstiian half ofwhat itisbeyond. 620 mu. Its diffusioncam beiprevented by addition to the emulsion. of the. basewdescribed in Example 2 of U. S. Patent 231L184, The. dye. bleaches very wellin the. presence of a silver image, leaving no stain.

. If,',in the above example; the N-ethyl -g'ammaa dye molecule permit linking of two nucleii A, B

or of two nuclei 3-3 by means of an external bond. It is possible in some cases to have the external bond preformed before the-coupling acid is replaced by-a N-alkyl-gammaeacid' witha.

.long-alkyl chain, such as hexadecyl-gamma-acid,

the dye becomes non-diffusing, renderingunnec essary the presence of a precipitating agent withoutharming its other qualities.

It is. further possible: to replace one or"botlr ethyl gamma-acid units in the above dye with NJZ-aminoethyl)-gamma-acid. The dyes thus.

takes place. In most cases, however,.it is; pref- I erable to link the finished monomeric disazo dye, as it is easier in this manner to arrive at apure end product.

Suitable external linkages are: CO=-,,-CS=, CX2 (where X is hydrogen, alkyl' or;ary l) is a bivalent hydrocarbon residue) and the like. These external linkages or heteronuclear-K bonds bind several azo units togetherwithoutfchanging essentially: the color of the corresponding monomeric dyes, as the resonance system is interrupted by said bonds. ,For example, the dye (e--A'N=NBN:N-'A )'z has" the optical properties of a disazo dye, even ifi'Z is a large number. Some of the mentioned linkages such as --SO2- are preferably present in:

the starting materials from which the dyes are I prepared. Other linkages such as --NH--CO-NH- Example, 1" The. dye:

obtained which contain one or" -two"-- terminal aliphatic amino, groups; can bereactedjwith alder hyd'es; isocyanates such as phenyl isocyanate, car

bonyl. chloride, acid chlorides; and. other; com

pounds, in order. to arrive atnon-wanderingrdyea U Example-a The-dyeis obtained in the following way: 2-amino-5- nitrohydroquinone dimethyl other is diazotized and coupled with acetyl-Heacid. "Ihe. -dye-. -ob= tained istreduced. withsodium, sulfide; or with ferrous sulfate; in. alkalinev solution, diazotized and coupledin-aqueouspyridine with l-'.(.4-sulfo=- phenyl) -pyrazolone- (5,) -3-carbonic:-acid (tartrae zinogenic sulfonic. acid). Itv dyes the-.gel'atine emulsion abrilliantblue-green shade, bleaches very-well, and has practically no desensitizing, effect on a red sensitive emulsiom The diffusion of the; dyein the above examplecanbe practically eliminated by varying, its constituents in a, suitable manner. One molf of tartrazinogenic acid-in the above example: can beireplacedzby half 2; mol' of 1,1-l2,2 disulfo-diphenylene (4,4') -bis- [pyrazolone- (5)'-carbonic= acid- (-3) and/or; one mol of acetyl-H'-acid'-- inthefabove described dye can be replaced-by-one half'mol Of adipyl-bis-H-acid, by; one mol of:heptfanoyl K-acid'or by one moi of octanoyI-J acidL" Example tating agent in the gelatin; emulsionbeccnies g V 1 unnecessary. The same result canbe reached by wsomefurther dyes arelisted in the following modifying the acyl radicals in the azo coupler table;. components of the above dye, 1. 'e., the toluene- No. 'A--N='N ".B -N=N-A Color 1.-. '8 p-tclnene-sulionylamino- 1,4-pl1ei.iylene .I8-1)-toluene-smllonylz=.cuino-u'blue.

l-hydroxy-afi-disulfo- I --1-h ydroxy-3,6disulfo- 'na' hthelene-Z-azo. i naphthalene-2-azo. 1 2,6-dichloro-l,4- do blue-violet.

phenylene. 6-sullo-1,4- naphblue-green. thglene. L i 2,5- ietlioxy-lA- do Do. phenylene. do 2-naphthol-l-azo Do. do 2-hydroxy-3,6-disulfonapli-. .Do

thalene-l-azo. lA-phenylene. 8-amino-1-hydtoxy-5-su1foblue.

- I naphthalene-2mm. I r .do G-amino-l-hydroxy-B-sulfo- Do.v

5 (2', 5 dichlorophenyl azo)nephthalene-2- azo. 2,5-dimetboxy-L4- 1-hydroxyphenyl-4 -azo; violet.

phenylene. I p

d 1 -hydroxy-5-amino-2-sulfoblue. pheny1-4-azo. 1-hydroxy-3-(3-sulfobenzoyl Do.

or 3-earboxylbenz e n esulfo)-phenyl-4-azo. G-phenylamino-l-hydroxy-3- blue-green.

sulfonaphthalene-2-azo. l-amino-7-sulfonaphthalene- Do.

-azo. 1 I 1 -hydroxy -6(8' p toluene Do. sulionylamino-l-hydroxy- 1i 7 3,6-disulfonaphthalenev V 2-azo-)-3-sulionaphtha-. Y I lene-Z-azo. 1-5. 12-hydr0xy-3,6-dlsnlfonaph- 3-sulfo-l.4-nap hl -hydroxynaphthalene-4- blue.

thalene-l-azo. thylene. azo. 16.. 1-phenylaminc-B-sulionaph- 1,4-phenylene.-. l-phenylamino-s-sulfonaphviolet.

thalene l-azo. v thalene-4-azo. .17.. 1-(4-snlfophenyD-pyra- .do l-(4-sulfophenyl)-pyra-. magenta.

' iolone-(5)-3-carbonic acid Zolone(5)-3-carbonic acid- -szo. am. 18.. l,8-dihydroxy-3,6-disulfo- 2-sulio-1,4-naphl,8-dlhydroxy-3,6-disulioblue.

naphthalene-2am. thylene. naphthalene-2am. 19.. Z-hydroxynaphthalene-l-azo 1,4-phenylene 2-hydroxynaphthalene-l-azo. magente. I 20.. l-hydroxy-8-chloro-3,6-dil,-i-phenylene-2,5- l-hydroxy-8-chlor0-3,6-diblue-green.

sulfonaphthalene-Z-azo. (diliigxyacetlc sulfonaphthalene-Z-azo.

. ac 21-. 2-amino-8-hydroxy-6-sn1io- 3-sulfo-1,4-plienyll-hydroxy-phenyM-azo purple.

na hthalene-l-azo. ene. 22.- o 2-sulfo-5-methoxyl-methylamino-phenyl-iblue.

. 1,4-phenylene. azo. 23.. Z-ethylamino-B-hydroxy-fi- 2,5-dichloro-l,4- 2-(3-chloro-2-hydroxy-n- Do.

sulfonaphthalene-l-azo. phenylene. propyl) -amino-8 hydroxyfi-snlfonaphthalene-l-azo.

I Emmpze 4 sn f H acid and the acetyl Kacid can be replaced, by heptanoyl l-l-acid, SebacyI-bis-H- 12 ml. of a 2% solution of the dye acid, 2,4 dichlorobenzoylel-l acid, octano yl-fK- CHI-GSOPNH OH OOHi' OH NH- co-Cm- N=N N= NaOa SOsNa CH NaOiS AOaNa acid and the likeI' It 'is' remarkable that even the dyes containing long chain aliphatic substituents are quite water soluble, of a good brilliancy, and

and 8 m1. of a 3% solution of diphenylenedibiguanide' acetate (U. S. Patent 2,368,647) are incorporated into 100 ml. of an ordinary silver halide gelatin emulsion. The whole is thoroughly mixed at 40 C. 'vvithdne precaution that the precipitated dye does not separate out. The resuitant emulsion is sensitized to red light by addition of a suitable sensitizer, coated on an opaque support andused for the bottom layer of-a multi-layer material.

The dyein the above example can be prepared by coupling 2--oxa1ylamino-5-amino-hydroqui-- none dimethyl ether with p-toluenesulfo-H- acidysplitting oil the oxalyl group, andcoupling the resulting amino azo dye with aoetyl-K-acid;

Ifthe methyl radicals in the methoxy groups of the above dye are replaced by other radicals, e.,g.,;butyl, hexyhbenzyl 0r aromatic radicals, the resulting dyes become less diffusing, and with some suitableradicals the presence .of aIp'recipibleach to a pure white where axsilver image is present.

If, in the dye of the above example, acetyl-J- acid replaces acetyl-K,-acid,- and H-acid (or. seacidior SS-acid) replaces toluenesulfo-H acid, a dye results which likewise has a very brilliant. blue-green color, and bleaches very well.

In addition to their use in emulsion layers as described, the dyes as defined in the following claims are equally suitable for use in light screening layers. These dyes can be' employed in filter overcoats or interlayers, in photographi'c'iilms, plates or paper. They can be usedto' dye up finished gelatin layers by bathing in'the dye solution, or they can be used to dye up'organic resins which afterwards may-be dispersed in p'hotographicfcolloids, a dfthey can be miiid with opaque white pigments. single layer or multi-layen coatings, or-in multiclayer coatings on one or both sides of a support.

containing these dyes may be 'coatedon trans- .parent fi1m supports-such as-a derivative of cel- ,lulose including cellulose esters and cellulose others, as well as on synthetic resin supports such as polyvinyl acetal and opaque supports .such :as paper or cellulose derivatives mixed with They may be used in Dyes of the general structure which we have described,=have remarkably brilliant shades and have-little adverse-effect upon the sensitivity of the emulsion in which they are incorporated or on 'adjacent emulsion layers; They can be destroyed in the presence of a silver image with suitable bleaching solutions, such as described'in U. S. Patents 2,020,775, 2,410,025 and others, and when used in filter layers they can be discharged by reduction.

Other variations of our invention are possible, and it is to be understood our invention is to be considered as limited only by the scope of the ap ended "claims. 4

-1. Aphotographio materialhaving at least one light sensitive silver halide layer, comprising a colloid 'layer dyed "with -a dye having the general immms wh'e'rein B is a member selected from the group .co'nsisting oi monocyclic and polycyclic aromatic residues in which the azo bonds shown stand in the 1, 4 position of said aromatic residue, and wherein A and A are residues of azo coupling components, which azo coupling components icarry-asubstituent selected from the group consisting of hydroxy, amino, monoalkylamino and arylamino radicals, which substituent is in a position selected from the group consisting of positions 2and 4 with respect'to the azo group.

. 42;- A photographic material having at least one light sensitive silver halide layer, comprising a colloid layer :dyed with a dye having the general tor-mule o -r n n iea mz I wherein B is a member selected from the group consisting of monocyclic and polycyclic aromatic residues in which the azo bonds shown stand in the 1, 4.position of said aromatic residue, wherein A and A" are residues of azo coupling components, which azo coupling components carry a substituentslected from the group consisting of hydroxy, amino, monoalkylamino and arylamino radicals, which substituent .is in a position selected from the group consisting of positions 2.iand 4 withrespect to theazo group, and wherein r il f and yv-aie selected from the group consisting o1 hydrogen and external linkages and e and .g are invpositions other than the 2 and 4position with .r'espec't to theazo groups and wherein Z represents an integer.

'3. Aphotograph ic.materialhaving at least one l'ight's'ens'itive silver halide layer, comprising .a colloid layer dyed with a dye having the general formula wherein B is a member selected from the group consisting of monocyclic and polycyclic aromatic residues in which the azo bonds shown stand in the 1,4 position of-saidaromatic residue, wherein A and A stand iormembers selected from the group consisting of aromatic and heterocyclic radicals, wherein a and a are in a .position selected from the group consisting of positions 2 and 4 with respect to the azo groups and-are radicals selected from the group consisting of hydroxy, amino, mono-alkylamino and arylamino radicals, wherein b, c, b and -cf-are inpoSi-tiohs other than the 2 and-4 position 'wi'thlrespect to the azo groups and are radicals selected groin the group consisting of hydrogen, carboxyl-"and sulfonic acid radicals and salts'of said carbo-xyl and sulfonic acid radicals, and wherein "d and d are in positions other than the '2 and 4 position with respect to the azo groups and-are-radicals selected from the group consisting of hydrogen, hydroxy, alkoxy, halogen, amino, alkylamino, arylamino, acylamino'and arylazo radicals.

4. A photographic material having at least one light sensitive silver halide layer, comprising a colloid layer dyed with a dye having the general formula wherein -b, c, :b" and c are in positions other than the 2 and 4 position with respect to the azogroups and are radicals selected iromthe group consistingof hydrogen, carboxyl and sulfonic acid radicals and salts. ofsfaid "carboxyi and suironic 'acid radicals, and wherein it and d. "are in positions other'thanjth'e 2 and 4'position withrespeot to the am groups and are' radicals selected'f am the group consisting" of hydrogen, hydroky, 'alkoiiy, halogen, amino, alkylam'ino, arylamino, acylamin'o and arylaz'o radicals. H 5. A photographic material having at least-one light sensitive silver halide layer, comprisng (a. colloid layer dyed with a dye having the general formula :A-N=NB-'-'-N==N--A wherein B is a member selected from the group consisting of i'nonocy'clic and polycyclic aromatic residues inwhich the azobonds shown stan'd'ih the '1, 4 position of said aromatic refs'idueahd wherein A and A 'repr e'sent sub'stituted naphthalene radicals having a radicaljselected from the group consisting of hydroxy, amino, inane alkylamin'o and arylamino radicals as a substi tuent in a position selected from the group consisting of positions '2 and -4 with respect to the azo groups.

B, Aphotogr'ap hic matr'iai naving atlasft 11 light sensitive silver halide layer, comprising a colloid layer dyed with a dye having the general formula wherein B is a member selected from the group consisting of monocyclic and polycyclic aromatic residues in which the azo bonds shown stand in the 1, 4 position of said aromatic residue, and

I wherein R stands for the residue of naphthalene in which the OH radical shown is in ortho position to the azo bond linked to said naphthalene residue, S is a member of the group consisting of 'Hand -SOa-cation, a: is an integer selected from the group consisting of l and 2, and A is a residue of an azo coupler having a hydroxy group in a position selected from the group consisting of positions 2 and 4 with respect to the azo bond wherein a, b, c and d are members selected from the group consisting of hydrogen, halogen, alkoxy groups, substituted alkoxy groups, aryloxy groups, alkyl groups, carboxyl groups, sulfo groups and members of a ring, and wherein A and A are residues of azo coupling components, which azo coupling components carry a substituent selected from the group consisting of hydroxy, amino, monoalkylamino and arylamino radicals, which substituent is a position'selected from the group consisting of positions 2 and 4 with respect to the azogroup.

8'. A photographic material having at least one light sensitive silver halide layer, comprising a .colloid layer dyed with a dye having the general formula wherein B is a member selected from the group consisting of monocyclic and polycyclic aromatic residues in which the azo bonds shown stand in the 1, 4 position of said aromatic residue, said member B carrying at least one ether residue in which the Q is linked directly to the aromatic residue, and wherein A is a residue of an aminonaphthol sulfonic .acid containing up to and including two sulfonic groups and in which the 1 light sensitive silver halide layer, comprising a colloid layer dyed with a dye having the general formula V A--N=NB-N=NA' wherein B is a member selected from the group consisting of monocyclic and polycyclic aromatic residues in which the azo bonds shown stand in the 1, 4 position of said aromatic residue, said member B carrying at least one ether residue in which the O is linked directly to the aromatic residue, and wherein A is a residue of an aminonaphthol sulfonic acid derived from a 1,8 aminonaphthol in which the hydroxyl group is in one of the positions 2 and 4 with respect to the azo group and containing up to and including two sulfonic groups, and A is a residue of an aminonaphthol sulfonic acid derived from a 1,8 aminonaphthol in which the hydroxyl group is in one of the positions 2 and 4 with respect to the azo group and containing up to and including two sulfonic groups, the amino group of at least one of said residues A and A being acylated with an acid selected from the group consisting of carboxylic and sulfonic acids.

10. A photographic material having at least one light sensitive silver halide layer, comprising a colloid layer dyed with a dye having the general formula I acyl HN OH NHacyl OH OR I MQNA S v S 5 wherein OR stands for an ether residue, acyl wherein B is a member selected from the group consisting of monocyclic and polycyclic aromatic residues in which the azo bonds shown stand in the 1, 4 position of said aromatic residue, and wherein A and A are residues of azo coupling components, which azo coupling components carry a substituent selected from the group consisting of hydroxy, amino, monoalkylamino and arylamino radicals, which substituent is in a position selected from the group consisting of positions 2 and 4 with respect to the azo group.

12. A photographic material having at least one light sensitive silver halide layer, comprising a filter layer having incorporated therein a dye having the general formula wherein B is a member selected from the group consisting of monocyclic and polycyclic aromatic residues in which the azo bonds shown stand in the 1, 4 position of said aromatic residue, and wherein A and A are residues of azo coupling components, which azo coupling components carry a substituent selected from the group con:- sisting of hydroxy, amino, monoalkylamino and arylamino radicals, which substituent is in a position selected from the group consisting of positions 2 and 4 with respect to the azo'group. 13. A photographic material having at least one light sensitive silver halide layer, comprising a colloid layer dyed with a dye having the general formula wherein B is an aromatic residue containing a benzene ring in which the azo bonds shown stand in 1, 4 position, and wherein A and A are residues of coupling components, which azo coupling components carry a hydroxy substituent in a position selected from the group consisting of positions 2 and 4 with respect to the azo group.

14. A photographic material having at least one light sensitive silver halide layer dyed with a dye having the general formula Aeyl H1? (1)11 O R Cation 02S 80;; Cation R0 wherein -OR stands for an ether residue in which R is an aliphatic radical, each acyl is a Cation 033- 10 sisting of hydroxy, amino, monoalkylamino and OH NH Acyl S Oa Cation arylamino radicals, which substituent is in a position selected from the group consisting of posi residue of a carboxylic acid at least one of said 20 tions 2 and 4 with respect to the azo group which acyl groups being the residue of a long chained comprises locally destroying said dye by reduction aliphatic carboxylic acid. in the presence of said metallic silver image.

'15. A process for producing a dye image in a photographic layer containing a metallic silver BELA image and dyed with a dye of the general formula PAUL DANIEL DREYFUsS- REFERENCES CITED The following references are of record in the file of this patent: I

UNITED STATES PATENTS 

1. A PHOTOGRAPHIC MATERIAL HAVING AT LEAST ONE LIGHT SENSITIVE SILVER HALIDE LAYER, COMPRISING A COLLOID LAYER DYED WITH A DYE HAVING THE GENERAL FORMULA
 15. A PROCESS FOR PRODUCING A DYE IMAGE IN A PHOTOGRAPHIC LAYER CONTAINING A METALLIC SILVER IMAGE AND DYED WITH A DYE OF THE GENERAL FORMULA 